The present invention relates to a thermoplastic elastomer composition and a process for producing the same and a hose using a thermoplastic elastomer composition and a process for producing the same. More specifically, it relates to a hose which includes a thermoplastic copolyester elastomer and a specific acrylic rubber and which, when these are used as the inner tube and/or outer cover of the hose, is superior in oil resistance, flexibility, cold resistance, and heat resistance and is capable of being produced, without requiring a vulcanization step, a thermoplastic elastomer composition and a hose suitable for various types of sealing agents, and processes for producing the same.
The present invention further relates to an olefin thermoplastic elastomer composition which gives a good adhesion to polyester fiber and, in particular, has a bondability capable of withstanding a stress caused by repeated deformation particularly at a high temperature of 120xc2x0 C. and a laminate having this as the adhesion layer or a structural layer, in particular a hose, and to a laminate superior in bonding formed by a layer of a thermoplastic elastomer composition composed of a polyolefin thermoplastic resin in which at least partially cross-linked elastomer component is blended and by a fiber reinforcing layer between which at least one thermoplastic adhesive resin selected from the group of maleic anhydride-modified polyolefin resin, epoxy-modified polyolefin resin, and polyester resin is interposed and which are bonded into an integral unit by hot melting and to a hose using the same.
The present invention further relates to a process for producing a hose composed of at least an inner tube composed of a thermoplastic material or flexible material and an outer cover composed of a thermoplastic material and a reinforcing layer, in particular relates to a process for producing a hose improved in durability of the hose by providing between the layers a bonding layer composed of a thermoplastic material and hot melting the bonding layer so as to form the bonding layer and reinforcing layer integrally and, in the production of a hose having at least an inner tube and a reinforcing layer composed of a reinforcing yarn, a hose braider provided with a heating means capable of improving the bondability of an inner tube composed at least at the outer circumference of the inner tube and the adhesive layer between reinforcing layers of a thermoplastic resin composition or thermoplastic elastomer composition or other thermoplastic resin material (hereinafter sometimes simply referred to as a thermoplastic resin material) with the reinforcing yarn braided on the outer circumference of the inner tube and the bondability of two or more reinforcing layers composed of reinforcing yarn and to manufacture a hose having flexibility and a high durability.
Rubber hoses are usually composed of an inner tube, a reinforcing layer, and an outer cover with the inner tube and outer cover composed of a vulcanized rubber. Such a rubber hose requires a vulcanization step, and therefore, there is the problem that the manufacturing process becomes complicated. On the other hand, there is known a so-called thermoplastic resin tube which is simpler in the manufacturing process thereof in the point that the inner tube and outer cover are composed of a thermoplastic resin and no vulcanization step is required. However, the thermoplastic resin comprising this resin hose is generally harder compared with vulcanized rubber, and therefore, it is difficult to obtain a flexible hose. In addition, the thermoplastic resin will soften by heating and therefore, it is usually difficult at a temperature of 120xc2x0 C. or more.
Therefore, attempts have been made in the past to improve the flexibility by adding, to the thermoplastic resin, amorphous polymers such as a rubber (for example, see Japanese Unexamined Patent Publication (Kokai) No. 5-25374, Japanese Unexamined Patent Publication (Kokai) No. 6-64102, and Japanese Unexamined Patent Publication (Kokai) No. 6-207086), but there is the problem that the compatibility of the thermoplastic resin with rubber is poor and, if the blending amount of the rubber is increased to improve the flexibility in an acrylic rubber (ACM)/thermoplastic copolyester elastomer thermoplastic elastomer material, where the ACM composition is EA (ethyl acrylate)=40, BA (butyl acrylate)=32, MEA (methoxyethyl acrylate)=19, GMA (glycidyl methacrylate)=9 (wt %), the elongation will fall and, as a result, the breaking energy will be reduced and, in turn, the problem will arise of the hose performance falling.
Further, to improve the flexibility of a thermoplastic resin, there is known a resin hose comprised of a polyester thermoplastic elastomer having an inner tube of polybutylene terephthalate as a hard segment and polytetramethylene glycol or polycaprolactone as a soft segment, but this polyester thermoplastic elastomer is limited in the extent to which the hardness can be reduced to obtain the necessary heat softening resistance and strength properties. It is not possible to obtain a hose having a sufficient flexibility and heat resistance like that of a vulcanized rubber.
Therefore, development of a hose having sufficient flexibility which can be produced by a simple process not requiring a vulcanization step and a hose provided with heat resistance as well enabling use for transmission of pressure or transport of liquids at a high temperature has been desired. In response to this, there has been proposed a hose having an inner tube and an outer cover comprising a thermoplastic elastomer composed of a thermoplastic resin in which a vulcanized rubber (see Japanese Unexamined Patent Publication (Kokai) No. 6-64102) is dispersed.
This hose has an inner tube composed of a thermoplastic elastomer composition comprising a thermoplastic copolyester elastomer in which a vulcanized composition of at least one acrylic rubber having an acryl group and epoxy group is dispersed and has an outer cover composed of a thermoplastic elastomer composed of a thermoplastic resin in which a vulcanized rubber is dispersed. Further, the reinforcing layer is composed of a rayon fiber, polyester fiber, or hard steel wire or other organic fiber or inorganic wire such as stainless steel wire bonded with the inner tube and outer cover via an ordinary temperature-curing type urethane adhesive, etc.
By this configuration, it is possible to obtain a hose which is flexible at ordinary temperature and does not require a vulcanization step, but this hose is not necessarily satisfactory in terms of the low temperature properties, in particular, the flexibility at low temperature and cold resistance. Furthermore, the improvement in the oil resistance has been required.
Further, the high pressure resin hoses for use in construction machinery etc. should preferably be improved in abrasion resistance, heat softening resistance, flexibility, etc. In particular, there has been a strong need for the improvement in the abrasion resistance, resistance to heat softening resistance, flexibility, weather resistance, etc. of the outer cover of the hose. Furthermore, regarding the abrasion resistance, there is vibration and rocking in the environments where hoses are used, and therefore, the surface of the outer cover of the hose often rubs against adjacent metal members etc. and is abraded. In the past, an ether based polyurethane or other thermoplastic resin having abrasion resistance was used for the outer cover of such a hose, but this was insufficient for long term use. Therefore, studies have been made how to improve the problem by the polymer structure, but there have been the defects of impairment of the flexibility. In this way, up until now, there has not been a thermoplastic elastomer composition which is superior in abrasion resistance, heat softening resistance, flexibility, etc. and can be suitably used for the outer cover of a hose.
In the past, in the bonding of an olefin thermoplastic elastomer composition and polyester fiber, no technique for stably bonding them, in particular, no olefin thermoplastic elastomer composition having a high temperature resistant bondability capable of withstanding, stress due to repeated deformation at a high temperature such as 120xc2x0 C. was known. This was because an olefin thermoplastic elastomer composition is a nonpolar substance and has a low surface energy, while a polyester fiber has polarity. Therefore, in general the bondability between the composition and the fiber is poor. In particular, it is not possible to maintain the strength of the bond at a high temperature.
To solve this problem, for example, a formulation using a so-called primer and adhesive system/adhesive resin has been proposed, but there is still not known an adhesive formulation or an olefin thermoplastic elastomer composition giving a bond of a strength capable of withstanding the repeated deformation at a high temperature such as 120xc2x0 C. In particular, in a hose, a dynamically vulcanized olefin thermoplastic elastomer composition has suitable properties as the outer cover material comprising the hose and a polyester fiber has suitable properties as a reinforcing fiber layer material comprising the hose, but there is not yet known an adhesive formulation for bonding the composition and the fiber, in particular, an adhesive formulation of a strength capable of withstanding the stress of repeated deformation at the environment of use of high pressure flexible hoses, that is, a high temperature such as 120xc2x0 C. No hose combining these materials is therefore known.
Accordingly, there has been a desire for an olefin thermoplastic elastomer composition having bondability with a polyester fiber and capable of withstanding the stress of repeated deformation at a high temperature such as 120xc2x0 C. and a laminate using the above thermoplastic elastomer composition and a polyester fiber.
There is known a hose comprising an inner tube, reinforcing layer, and outer cover laminated in that order. In this hose, the inner tube and outer cover are composed of a vulcanized rubber or urethane, polyester, or nylon, or other plastics and the reinforcing layer is composed of nylon, polyester, rayon, vinylon, or aromatic polyamide fiber or other fiber braided or wrapped in a spiral. Between these layers, bonding is performed using a rubber cement or urethane adhesive etc.
However, the so-called xe2x80x9crubber hosexe2x80x9d using rubber in the outer cover requires a vulcanization step, and therefore, the manufacturing process becomes complicated. Further, a so-called resin hose using just a thermoplastic resin for the inner tube and outer cover is hard and poor in flexibility and, when bent, has the problem of formation of kinks. As one proposal for solving this problem, there has been proposed a hose using a thermoplastic elastomer composition comprising a polyolefin based thermoplastic resin, polyvinyl chloride based thermoplastic resin, polyamide based thermoplastic resin, polyester based thermoplastic resin, or other thermoplastic resin in which an at least partially cross-linked vulcanized rubber phase, is dispersed (for example, see Japanese Unexamined Patent Publication (Kokai) No. 6-64102).
Among these thermoplastic elastomer compositions, a thermoplastic elastomer composition composed of a polyolefin thermoplastic resin and an at least partially cross-linked elastomer component blended therein, is high in flexibility and suitable as a material for the inner tube and outer cover of the hose. However, there has not yet been developed an adhesive exhibiting excellent bondability to both a fiber reinforcing layer composed of a polyester, nylon, rayon, or other fiber and a thermoplastic elastomer composition composed of a polyolefin thermoplastic resin and an at least partially cross-linked elastomer component blended therein.
For example, as methods for improving the adhesiveness of the main component of the thermoplastic elastomer composition, that is, the polyolefin thermoplastic resin, there are known corona discharge, UV irradiation, flame treatment, strong acid treatment, and other surface activation methods. With these methods, however, not only is it difficult to secure the level of bonding required for hoses and other durable products composed of a thermoplastic elastomer composition, but also the process of application to a manufacturing line of a hose is extremely complicated and very high in cost, and therefore, is not practical.
Further, elastomer compositions are used as various sealing agents, rubber hoses, and other industrial products and also for other rubber products. In particular, epoxy group-containing acrylate copolymer rubbers containing (meth)acrylic acid esters etc. are elastomer compositions known to be superior in oil resistance and aging resistance and, when cross-linked, cold resistance or strength properties as well. There is the problem, however, that a sufficient elongation and compression set resistance cannot be obtained with a conventional cross-linking agent (polyfunctional carboxylic acid).
On the other hand, in recent years, thermoplastic elastomer compositions provided with both the advantages of a rubber and thermoplastic resin have been developed using the dynamic vulcanization (dynamic cross-linking) of rubber, but when selecting an acrylate copolymer as the rubber component, in particular when using an epoxy group as the cross-linking site of the acrylate copolymer so as to obtain an elastomer composition not including an amine component, since an amine component would promote the deterioration of the polyester, there is the problem that a sufficient elongation and compression set resistance cannot be obtained. For example Japanese Unexamined Patent Publication (Kokai) No. 1-92251 discloses a rubber composition composed of an ethylene copolymer rubber and acrylic rubber offering a balance of cold resistance, oil resistance, resistance to aging by heat, and strength properties. Further, Japanese Unexamined Patent Publication (Kokai) No. 5-25347 discloses a high stress resistant thermoplastic elastomer composition composed of a thermoplastic copolyester or copolyamide elastomer and epoxy-containing (meth)acrylate copolymer rubber which is flexible and gives a superior heat resistance and compression set resistance.
Further, Y. Tsukahara et al, International Rubber Conference Full Texts, p. 74 (1995) and Japanese Unexamined Patent Publication (Kokai) No. 7-304902 disclose a natural rubber composition as an environmentally friendly elastomer material composed of epoxylated natural rubber and terminal carboxylated polycaprolactone which is excellent in fluidity and is superior in the elastic modulus of the rubber, elongation, and oil resistance.
As explained above, these various elastomer compositions and thermoplastic elastomer compositions have superior performance, but have the problem that a practically sufficient elongation and compression set resistance cannot be obtained.
The present inventors previously proposed a hose having at least an inner tube, reinforcing layer, and outer cover, where the inner tube is a thermoplastic elastomer composition having a structure of a matrix of a thermoplastic copolyester elastomer and vulcanized rubber particles of an acrylic rubber having an acryl group and epoxy group dispersed therein and containing 30 to 90% by weight of the thermoplastic copolyester elastomer component and 70 to 10% by weight of the vulcanized rubber component of the acrylic rubber, the reinforcing layer is composed of a polyester fiber etc., the outer cover is a thermoplastic elastomer having a structure of a matrix of a thermoplastic copolyester elastomer and vulcanized rubber particles of an acrylic rubber having an acryl group and epoxy group dispersed therein and containing 30 to 90% by weight of the thermoplastic copolyester elastomer component and 70 to 10% by weight of the vulcanized rubber of the acrylic rubber component, and an adhesive is disposed at least between the reinforcing layer and the outer cover (Japanese Patent Application No. 8-23903). That is, they proposed a hose wherein, by selection of the material of the inner tube and outer cover of the hose, it was possible to improve the hose flexibility at ordinary temperature and low temperature, oil resistance, and cold resistance and further reduce the production costs by making it possible to produce it, without requiring a vulcanization step.
In this hose, however, a urethane ordinary temperature-curing type adhesive etc. are used as the bonding layer. Since the adhesive was a reactive type, heat curing occurred due to the heat during use, and therefore, the bonding layer became hard and in turn the filaments of the fibers of the reinforcing layer broke causing the reinforcing layer to break and the durability to fall. Even if using a polyester type hot melt adhesive resin in place of this, the adhesive resin detracts from the thermoplasticity and is poor in heat softening resistance, and therefore, a hose which is satisfactory in durability (high temperature impact pressure test: 120xc2x0 C., 27.5 MPa) cannot be obtained.
In the past, hoses composed of an inner tube, reinforcing layer, and outer cover with an inner tube and outer cover made out of a thermoplastic resin composition, thermoplastic elastomer composition, or other thermoplastic material have been capable of reducing production costs since they do not require a vulcanization step. These hoses have, therefore, come into wide use. In these conventional hoses, the bonding between the inner tube and the reinforcing layer and the bonding between reinforcing layers have been performed using moisture curing type urethane adhesives and other ordinary temperature-curing type adhesives or using copolyester resin or olefin resin or other hot melt type adhesive resins and heating after the formation of the inner tube, reinforcing layer, and outer cover so as to melt the adhesive resin and cause bonding. Further, hoses which use a high rigidity thermoplastic resin for at least one of the inner tube and outer cover, whereby do not require bonding of the inner tube and reinforcing layer or bonding between the reinforcing layers are being used.
However, with a hose using an ordinary temperature-curing type adhesive, since the adhesive is a reactive type, it cures with heat during use. The bonding layer becomes hard and, when the hose is subjected to repeated bending or pressure changes, the hardening of the bonding layer causes the fibers of the reinforcing layer to break and causes a problem in the durability of the hose. Further, if a hot melt type adhesive resin is used, due to the limitations in the order of formation of the layers, with ordinary processes of production, there is no bond between the bonding layer and the layer above it, and therefore it is necessary to heat the bonding layer to cause it to bond with the layer above it. Since this means heating from the outside of the hose after the formation of the outer cover until the adhesive resin melts, an excessive amount of heat is given to the hose. This causes dimensional changes in the hose or uneven tension to the fibers of the reinforcing layer, whereby the uniformity of the hose is impaired and sufficient durability is made impossible. Further, in recent years, there have been strong demands for making hoses more flexible for the purpose of hose attachment, but a hose using a low rigidity (or flexible) thermoplastic material for the inner tube and not having the layers bonded to each other has problems in terms of its durability, and therefore, large problems in use. Further, in the case of an ordinary temperature-curing type adhesive, an organic solvent is used, and therefore, there are problems in terms of the environment. In the case of a hot melt type adhesive, there are problems in the productivity due to the heat treatment step after the formation of the outer cover.
In the past, further, a high pressure hose has, for example, been composed of an inner tube having a thermoplastic resin material for at least the outer circumference of the inner tube, at least one reinforcing layer composed of reinforcing yarn braided around the outer circumference of the inner tube, and an outer cover covering the surface of the same. In such a hose, however, the bondability between the inner tube having a thermoplastic resin material for at least the outer circumference of the inner tube and the reinforcing yarn braided around the outer circumference of the inner tube and the bondability between two or more reinforcing layers has a major influence on the flexibility and durability of the hose. If the bondability is poor, the inner tube and the reinforcing yarn will separate or the reinforcing layers will separatexe2x80x94adversely influencing the performance of the hose. In the past, the reinforcing yarn was braided around the outer circumference of the inner tube composed of the thermoplastic resin material or, further, when there were two or more reinforcing layers, a solvent based adhesive was used, the reinforcing yarn braided around the outer circumference of the inner tube, and the reinforcing layers bonded. There were also cases of use of means other than solvent type adhesives such as the use of infrared rays, far infrared rays, near infrared rays, ultrasonic waves, high frequency heating, electrical induction heating, etc. to heat an inner tube composed of a thermoplastic resin material or an adhesive resin layer composed of a thermoplastic resin material arranged between two or more reinforcing layers after the formation of the hose by an oven or other heating apparatus from the outer surface of the outer cover so as to bond the inner tube and the reinforcing yarn or the reinforcing layers. When a solvent type adhesive is used, however, there tend to be problems in safety and health or problems of pollution due to the evaporation of the solvent, one or two days are required for the aging for achieving a practical strength, and it was difficult to improve the productivity. Further, in the case of the latter method of using a heating apparatus, the component parts have been subjected to aggravated dimensional changes, aging, etc. and therefore, the effect on the quality has been high (heating of just the surface of the target object has been impossible), there have been limitations as to the installation space, the equipment has been high in price and large in size, and there have been other problems. Therefore, it is clear that there have been many problems in the method of bonding the above conventional inner tube and the reinforcing yarn or the bonding between reinforcing layers.
Accordingly, an object of the present invention is to provide a thermoplastic elastomer composition which, when used for the inner tube and/or outer cover of a hose, enables the improvement of the hose flexibility at an ordinary temperature and low temperature, oil resistance, and cold resistance and enables reduction of the production costs since no vulcanization step is required and a hose using this composition for the inner tube and/or outer cover and having the above properties.
Another object of the present invention is to provide a thermoplastic elastomer composition having a stable mixability and high elongation at break and a hose using the same.
A further object of the present invention is to provide a thermoplastic elastomer composition which has a larger elongation and smaller compression set compared with a conventional elastomer composition or thermoplastic elastomer composition and simultaneously achieves a flexibility and breakage resistance enabling use for the inner tube or outer cover of a high pressure hose such as an oil pressure hose.
A further object of the present invention is to provide a thermoplastic elastomer composition which reduces the abrasion coefficient of the hose outer cover, gives a superior abrasion resistance of the hose surface, is superior in heat softening resistance, flexibility, etc. and is suitable for use as a high pressure plastic hose, a process for producing the thermoplastic elastomer composition, and a hose using the same as the outer cover.
A further object of the present invention is to provide an olefin thermoplastic elastomer composition which has excellent bondability with a polyester fiber and is superior in the heat resistance, a laminate of the same, and a hose using the same.
A further object of the present invention is to provide a process for producing a hose which is superior in durability, is flexible, is low in production costs, and is environmentally problem free and to provide a braider for a hose which enables reliable bonding of the inner tube and reinforcing yarn or reinforcing layers, without the use of a solvent type adhesive or high cost facilities, enables efficient production, and enables improvement of the productivity of a hose with flexibility and a high durability.
In accordance with the first aspect of the present invention, there are provided a thermoplastic elastomer composition comprising (i) 30 to 90% by weight of at least one thermoplastic copolyester elastomer and (ii) 10 to 70% by weight of a rubber component comprising at least one acrylic rubber having an acryl group and an epoxy group, provided that the total weight of the components (i) and (ii) are 100% by weight and a hose using the same as an inner tube and/or outer cover.
In accordance with the first aspect of the present invention, there is also provided a thermoplastic elastomer composition comprising a matrix of at least one thermoplastic copolyester elastomer and vulcanizing rubber particles of at least one acrylic rubber having an acryl group and an epoxy group dispersed in the matrix wherein the viscosity xcex71 and volume fraction xcfx861 at the processing temperature (or mixing temperature) of melt mixing of the thermoplastic copolyester elastomer and the viscosity xcex72 and volume fraction xcfx862 at the time of melt mixing of the acrylic rubber in the unvulcanized state in the absence of a vulcanization agent at the range of a temperature of 180 to 350xc2x0 C. and a shear rate of 1000 to 8000 sxe2x88x921 satisfy the following formulas.
0.25xe2x89xa6xcfx861xe2x89xa60.90
0.10xe2x89xa6xcfx862xe2x89xa60.75
xcfx861+xcfx862xe2x89xa61.0
xcex72/xcex71 less than 4.0
(xcex71/xcex72)(xcfx862/xcfx861) less than 1.0
and a hose using the same for the inner tube and/or outer cover.
In accordance with the second aspect of the present invention, there is provided a thermoplastic elastomer composition comprising at least one acrylic rubber having an acryl group and an epoxy group and a polycaprolactone having a carboxyl group at the end thereof in an amount of 5 to 30 parts by weight based upon 100 parts by weight of the copolymer rubber (phr).
In accordance with the second aspect of the present invention, there is also provided a thermoplastic elastomer composition comprising (i) 30 to 90% by weight of a thermoplastic resin component composed of at least one thermoplastic copolyester elastomer, (ii) 10 to 70% by weight of a rubber component comprised of at least one acrylic rubber having at least one type of acrylic group and epoxy group, and (iii) 5 to 30 parts by weight, based upon 100 parts by weight of the rubber component, of a polycaprolactone having a carboxyl group at the end thereof as a cross-linking agent wherein the rubber component forms a dispersed phase and the thermoplastic resin component forms a continuous phase.
In accordance with the third aspect of the present invention, there is provided a thermoplastic elastomer composition comprising a thermoplastic elastomer composition composed of at least (i) a polyester thermoplastic resin and (ii) a vulcanized rubber composition of an acrylic rubber having an acryl group and an epoxy group dispersed therein wherein (iii) an epoxy-modified olefin polymer having of the following formula (I):
"Parenopenst"(A)"Parenclosest"x"Parenopenst"(B)"Parenclosest"y"Parenopenst"(C)"Parenclosest"zxe2x80x83xe2x80x83(I)
wherein, A represents an acrylate unit, B represents an epoxy group unit, and C represents an olefin unit, x, y, and z are the molar percentages in the epoxy-modified olefin polymer, provided that x+y+z is 1, the acrylate unit A(x), epoxy group unit B(y), and olefin unit C(z) being essential components and the epoxy group unit B being contained in a molar percentage y of 0.005 to 0.200, and the component (i) being 90 to 30 parts by weight and the component (iii) being 1 to 25 parts by weight when the total weight of the components (i) and (ii) is 100 parts by weight.
In accordance with the third aspect of the present invention, there is also provided a hose having at least an inner tube, reinforcing layer, and outer cover wherein the above thermoplastic elastomer composition is used for at least one of the inner tube and outer cover.
In accordance with the fourth aspect of the present invention, there is provided a thermoplastic elastomer composition superior in abrasion resistance comprising (i) a rubber composition of (A) at least one silicone selected from the group consisting of organosiloxanes and their modified forms, (B) a copolyester thermoplastic resin, (C) an acrylic rubber, and (D) a vulcanizing agent for the rubber composition, wherein vulcanized rubber particles of the rubber composition are finely dispersed in the thermoplastic resin.
In accordance with the fourth aspect of the present invention, there is also provided a process for producing a thermoplastic elastomer composition comprising the steps of, in the production of the thermoplastic elastomer composition;
blending the thermoplastic resin (B), the rubber composition (C), and the vulcanization agent (D) to produce a thermoplastic elastomer composition composed of all the components other than the silicone; then
blending the silicone (A) therewith.
In accordance with the fourth aspect of the present invention, there is also provided a hose comprising at least an inner tube, reinforcing layer, and outer cover, wherein the thermoplastic elastomer composition is used for the outer cover.
In accordance with the fifth aspect of the present invention, there is provided a thermoplastic elastomer composition superior in bondability with an olefin thermoplastic resin, a polyester thermoplastic resin, and a polyester fiber containing the following components A, B, and C:
Component A: an olefin thermoplastic elastomer composition composed of an olefin thermoplastic resin (a), as a matrix, wherein particles of a vulcanized ethylene-propylene-diene copolymer (EPDM) rubber composition (b) is finely dispersed therein and containing 85 to 20% by weight of the olefin thermoplastic resin and 15 to 80% by weight of the vulcanized EPDM rubber composition
Component B: a polyester copolymer resin
Component C: an epoxy group-containing thermoplastic resin in a ratio of 90 to 50 parts by weight of the component A, 10 to 50 parts by weight of the component B, and 1 to 10 parts by weight of the component C, based upon 100 parts by weight of the total amount of the components A and B.
In the above thermoplastic elastomer composition, the epoxy group-containing thermoplastic resin preferably contains at least 60 to 95% by weight of a component from an ethylene monomer and 0.5 to 15% by weight of a component from glycidyl methacrylate.
In accordance with the fifth aspect of the present invention, there is also provided a laminate comprising at least the thermoplastic elastomer composition of the present invention and a polyester fiber bonded by melt bonding, in which laminate, the melt bonding of the thermoplastic elastomer composition of the present invention and the polyester fiber may also melt bonded through a polyester copolymer resin.
In accordance with the fifth aspect of the present invention, there are also provided a hose comprising at least an outer cover adjacent to a polyester fiber reinforcing layer wherein at least the innermost layer of the outer cover is formed from a thermoplastic elastomer composition of the present invention,
a hose comprising at least a polyester fiber reinforcing layer bonded through a bonding layer to an outer cover wherein the bonding layer is a polyester copolymer resin and at least the innermost layer of the outer cover is formed from a thermoplastic elastomer composition of the present invention, and
a hose comprising at least a polyester fiber reinforcing layer bonded through a bonding layer to an outer cover wherein the bonding layer is formed from a thermoplastic elastomer composition of the present invention and at least the innermost layer of the outer cover is formed from a thermoplastic elastomer composition composed of an olefin thermoplastic resin as a matrix and a vulcanized EPDM rubber composition as a domain.
In accordance with the sixth aspect of the present invention, there is provided a laminate superior in bonding formed by a layer of a thermoplastic elastomer composition composed of a polyolefin thermoplastic resin, in which an at least partially cross-linked elastomer component and a fiber reinforcing layer, between which at least one thermoplastic adhesive resin selected from the group consisting of a maleic anhydride-modified polyolefin resin, epoxy-modified polyolefin resin, and polyester resin is interposed, which are bonded together by hot melting, to a hose using the same.
In accordance with the seventh aspect of the present invention, there is provided a hose comprising at least an inner tube, reinforcing layer, and outer cover wherein the inner tube is a thermoplastic elastomer composition having a structure of, as a matrix, a thermoplastic copolyester elastomer in which is dispersed vulcanized rubber particles of an acrylic rubber having an acryl group and an epoxy group and containing 30 to 90% by weight of the thermoplastic copolyester elastomer component and 70 to 10% by weight of the vulcanized rubber component, of the acrylic rubber the reinforcing layer is composed of a polyester fiber, the outer cover is formed from a thermoplastic elastomer comprising, as a matrix, a thermoplastic copolyester elastomer in which vulcanized rubber particles of an acrylic rubber having an acryl group and an epoxy group is dispersed and containing 30 to 90% by weight of the thermoplastic copolyester elastomer component and 70 to 10% by weight of the vulcanized rubber component of acrylic rubber and a bonding layer is disposed between at least the reinforcing layer and outer cover, wherein the bonding layer is formed from a thermoplastic resin composition containing at least 50% by weight of a thermoplastic polyester copolymer resin where the dicarboxylic acid constituting the polyester is an aromatic dicarboxylic acid and the Young""s modulus at 120xc2x0 C. is at least 3.0 MPa.
In accordance with the preferred embodiments of the seventh aspect of the present invention, there are also provided a hose wherein the thermoplastic polyester based copolymer resin in the bonding layer has a melt viscosity, at a temperature of 230xc2x0 C. and a shear rate of 50 to 200 sxe2x88x921, of not more than 1000 Paxc2x7s and
a hose wherein the thermoplastic polyester copolymer resin of the bonding layer is a thermoplastic block copolyester elastomer composed of recurring units of a polyester and polyether or recurring units of a polyester and polyimide ether and containing at least 40 mol % of recurring units of the polyester.
In accordance with the eighth aspect of the present invention, there is provided a process for producing a hose comprising an inner tube and outer cover composed of a thermoplastic material and one or more braided or spiral structure reinforcing layers composed of a fiber formed between the same, comprising the steps of forming the outer cover, heating the outer surface of the inner tube by a heating means to at least the softening temperature of the thermoplastic material to convert the outer surface of the inner tube to a molten state, whereby the bond between the inner tube and reinforcing layer is strengthened.
In accordance with the ninth aspect of the present invention, there is provided a braider for the manufacture of a hose comprising at least an inner tube and a reinforcing layer composed of a reinforcing yarn wherein at least the outer circumference of the inner tube is composed of a thermoplastic resin material, which braids a reinforcing yarn on the outer circumference of the inner tube, wherein a braiding die of the braider is provided with a heating means for continuously heating the surface layer of the inner tube in the step immediately before braiding the reinforcing yarn over the inner tube.
In accordance with the second embodiment of the ninth aspect of the present invention, there is provided a braider for the manufacture of a hose comprising at least an inner tube and at least two reinforcing layers composed of a reinforcing yarn and having an adhesive resin layer composed of a thermoplastic resin material between the reinforcing layers, which braids a reinforcing yarn on the outer circumference of the inner tube, wherein a braiding die of the braider is provided with a heating means for continuously heating the surface layer of the adhesive resin layer in the step immediately before the braiding of the reinforcing yarn over the adhesive resin layer.